Acid monoazo dyestuffs



United States Patent 3,116,280 ACID MONUAZQ DYESTUFFS Franz Frisch, Porza, Tessin, and Carl Rytlel, Dornaeli, Solothurn, Switzerland, assignors to Sandoz Ltd. (also known as Sandoz All), Basel, Switzerland No Drawing. Filed Jan. 16, 1961, Ser. No. 82,686 Claims priority, application Switzerland Jan. 22, 196i) 3 Claims. (Cl. 260-199) This invention relates to acid monoazo dyestuffs of the formula S O 3H (1) ROO CHN (11) wherein R represents a hydrocarbon radical which is bound to the carbon atom of the carbonyl group through an oxygen atom and contains at least carbon atoms and may be substituted, wherein the radical ROOC HN stands in 4- or S-position and the nucleus A may contain further substituents, with 1 mol of an azo component of the formula Nrrl B I-IOsS- wherein X has the forccited meaning and the nucleus B may contain further substituents, or (b) reacting a monoazo dyest-ufi? of the formula I S 0 3H (IV) wherein X, A and B have the aforecited meanings and the N5 group stands in 4- or 5-position, with a functional derivative of an acid of the formula R-O--COOH wherein R has the aforecited meaning.

ddl diid Patented Dec. 31, 1963 The new acid monoazo dyestufis dye wool, silk, leather and synthetic polyamide fibers from neutral to weakly acid baths in bright, bluish-red shades which have very good fastness to light and Wet treatments, especially to washing, perspiration, acid, alkali and alkaline milling.

The compounds of Formua H can be produced from the corresponding diarninobenzenesuifonic acid by monoacylation or from the corresponding aminonitrobenzenesulionic acid by acylation and subsequent reduction, for example from 2,4-diaminobenzene-l-sulfonic acid, 2,5- diaminobenzene-l-sulfonic acid, 2,4-diamino-5-methylbenzene-i-sultonic acid, 2,4-diamiuo-S-chlorobenzene-1- eulfonic acid, 2-nitro-4-aminobenzene-l-sulfonic acid.

it is possible to arrive at the dyestuil of Formula IV, for example, by diazotising a corresponding aminonitrobenzenesulfonic acid, coupling in acid medium with a compound of Formula Ill and reducing the nitro group to the amino group, or by diazotising a 4- or S-acylamino-laminobenzene2-sulfonic acid and coupling in acid meium with a compound of Formula Ill with subsequent saponification. Suitable starting products for this purposes are elg. 4-nitro-6-methyl-l-aminobenzene-Z-sultonic acid, 4-chloro-5-nitro-l-aminobenzene-6-sulfonic acid, 4- acetylor 4-iormylamino--lantinobenzene-Z-sulfonic acid, l-amino-3-propionylarnino-4-ethylbenzene-G-sulfonic acid.

For the reaction of the aminomonoazo compound of Formula 1V according to the present invention to give the dyestufi' of Formula 1, excellent acylating agents are the chlorotormie acid esters of aliphatic and aromatic alcohols which may be further substituted, such as anyl, hexyl, octyl, decyl, lauryl, cetyl, benzyl and cyclohexyl alcohols, and the chloroformic acid ester of the 4-octyland 4-cyclohexyl-l-hydroxybenzene.

As 2120 components of Formula Ill according to the invention, the following ar suitable: 2-(2,4-dimethyl)- phenylamino-, 2-(2',5'-dimethyl)-phenylamino-, 2-(2,6- dimetnyl)-phenylamino-, 2 (2,4,6'-trimethyl)phenylamino-, 2-(2-rnethyl)-phenylarnino-, 2(2-rnethyl-4,6'- dichloro)-phenylatnino-, 2 (2',6 dimcthyl-4-chloro}- phenylamino-, 2-(2-methyl-5-chioro)-phenylarnino-, 2- (2'-ethyl)-phenylaminoor 2-(2'-eth' -/l-5'-chloro)-phen lamino-S-hydroxynaphthalene-6eulfonic acid.

J. to starting materials of Formula ll used in the present invention are preferably diazotised indirectly.

Thanks to the high energy of coupling of the diazo compounds employed, the combination of the components proceeds fairly rapidly in the presence of mineral acid and in each case in l-position to the azo component, The coupling reaction can, of course, be accelerated when the mineral acid is practically neutralised by the careful, gradual addition of an acid-binding agent, e.g. sodium acetate. The monoazo dyestuffs formed, which are often veil crystallized, are filtered oil, it necessary by the addition of common salt, and dried.

As a rule, the introduction of the acyl radical is accomplished by dissolving the dyestuil to be acylated in aqueous medium, if desired with the addition of an organic solvent such as acetone or dioxane, and adding the acylating agent at a low or increased temperature, if necessary in the presence of an acidbinding agent such as sodium hydroxide solution, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium carbonate or pyridine, which at the same time can act as a catalyst.

In the following examples the parts and the percentages are by weight and the temperatures in degrees centigradc.

EXAMPLE 1 59.8 parts of the monoazo dyestulr" obtained by the acid coupling of 23 parts of diazotized l-aminor-acetylaminobenzene-2sulfonic acid with 35.7 parts of 2-(2',4,6'-trimethyl) phenyl-arnino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in the form of the disodium salt in a according to the rate of consumption. During acylation 10 10 parts of sodium bicarbonate are strewn into the reaction mass in small portions so that a constant pH value of 7.5-8 is maintained. The dyestuff thus formed is completely precipitated, and, after the reaction mass has cooled, it is filtered off with suction and dried. The new 1 monoazo dyestuif is a dark red powder which dyes Wool, silk and synthetic polyamide fibers from a neutral to Weakly acetic acid bath in full ruby shades of very good light fastness and excellent wet fastness.

Similar dyestuffs are obtained when the 25 parts of chloroforrnic acid lauryl ester are replaced by an equivalent amount of chloroformic acid octyl ester or chloroformic acid cetyl ester.

In the following table are listed further monoazo dyestuiTs which can be obtained according to the particulars given in Example 1. They correspond to the formula sour H0 /3 2 A 1 N=N The meanings of R, X and the substituents of the nuclei A and B are given in the column headings.

Table A Meaning of the substituents Meaning of R in the radical ROCHN in 4- or 5- Example in nucleus B position of nucleus A Shade of N o. the dyeing on Wool X 3 4 5 6 in 4-positi0n in 5-position H CH3 H CH CH3(CH2)1O H CH; H CH3 CH3(CH2)9O D H CH3 H CH3 CH3(CH2)i5O- H H H H CH3(CHz)9O- H OH; H H CH3(CHz)oO H H CH3 H CH3(CE2)11O H H H CH3 CH3(CH2)7-O H H H CH CH3(CH2)150 H CH3 H CH3 H CH H CH H CH3 H CH3 H H H H CH3(CHz)oO D0. H H H H CH3(CHz)4O Do. H H H H CH3(CH2)5O- Do. H H H H OH3(OH2)6O D0. H H H H CH3(OI-Iz)a-0 Do. H H H H CH3(CH2)17 D0. H CH3 H CH3 DO. H H H H D0.

G1 I 21 CH3 H CH3 H om c1-Qomo -l Do 22 cm H CH3 H 0113 CHz-O D0.

23 CH3 11 CH3 H CH3 o1 c1no- Do T able B Meaning of the substituents e.g. the radical R Meading oi the substituents in nucleus B in the radical R-O C-HN- in 4- position of Shade of Example N0. nucleus A the dyeing on wool X 3 4 5 6 in i-position 5- 6 11 H H H CH3 blue-red H H H H H Do. H H H H H De. II II 11 H H C1 D0. II H II II CHa(CI-I2)|2O H Do.

Meaning of the substitucnts e.g. the radical R-O C-HN- in s position of nucleus A in 5-position 4- 6- H H H H CH3(CH2)12O- 01 H Do. H H H H CH3 CH2)12O CH3 H D0. H H H H CHa(CH2)i2O H C1 D0.

Formulae of the representative dyestuffs of the foregoing examples are as follows:

Having thus disclosed the invention what we claim is: 1. Acid monoazo dye of the formula wherein R is a member selected from the group consisting of alkyl containing from to 18 carbon atoms, benzyl, monochlorobenzyl and trichlorohenzyl, w is a member selected from the group consisting of hydrogen, methyl, ethyl and chlorine, x is a lower alkyl each of y and z is a member selected from the group consisting of hydrogen and methyl,

wherein w stands in one of the positions 4, 5 and 6,

each of y and z stands in one of the position 4', 5 and 6 and the radical R-OOC-HN- stands in one of the positions 4 and 5. 2. The acid monoazo dyestuif which corresponds to the formula I SIOsH CH3 rncaonnyo-o O-HNC N=N 3. The acid monoazo dyestuff which corresponds to the formula E iOaH References Cited in the file of this patent UNITED STATES PATENTS Knight et a1 Apr. 17, 1945 Kappeler et al Sept. 15, 1959 

1. ACID MONOAZO DYE OF THE FORMULA 